CN112724497B

CN112724497B - Polyethylene laser marking master batch and preparation method and application thereof

Info

Publication number: CN112724497B
Application number: CN202011430053.9A
Authority: CN
Inventors: 宋晓庆; 黄险波; 叶南飚; 付晓; 刘乐文; 刘思杨
Original assignee: Kingfa Science and Technology Co Ltd; Guangdong Kingfa Science and Technology Co Ltd
Current assignee: Kingfa Science and Technology Co Ltd; Guangdong Kingfa Science and Technology Co Ltd
Priority date: 2020-12-09
Filing date: 2020-12-09
Publication date: 2022-08-19
Anticipated expiration: 2040-12-09
Also published as: CN112724497A

Abstract

The invention discloses a polyethylene laser marking master batch, and a preparation method and application thereof. The polyethylene laser marking master batch comprises the following components in parts by weight: 45-70 parts of a polyethylene matrix, 10-15 parts of a polystyrene-based copolymer, 15-30 parts of lamellar structure mineral particles, 5-10 parts of a compatilizer, 1-2 parts of a lubricant and 0.1-0.3 part of a crosslinking sensitizer; the silicon content of the lamellar structure mineral particles is more than or equal to 30 wt.%. The polyethylene laser marking master batch has excellent laser sensitivity. The polyethylene laser marking master batch is added into polyethylene according to the weight ratio of 5-10%, and the prepared polyethylene material is excellent in laser marking performance and can be used for preparing an optical cable sheath.

Description

Polyethylene laser marking master batch and preparation method and application thereof

Technical Field

The invention relates to the field of high polymer materials, in particular to a polyethylene laser marking master batch and a preparation method and application thereof.

Background

The traditional product marking technology mainly adopts ink transfer printing, code spraying and marking and the like, and has the advantages of wide color selectivity and wide applicable materials, but the technology has the defects of poor environmental friendliness, poor durability and the like. The laser marking is a novel environment-friendly marking technology, and mainly utilizes a laser beam with high energy density to act on a target, so that the surface of the target is subjected to physical or chemical change, and visible patterns are obtained.

According to the product requirements, the information such as product name, manufacturer, length and the like must be marked on the surface of the optical cable sheath at regular intervals. The optical cable sheath material is usually a high polymer material such as polyethylene, which has a very weak absorption degree for laser beams and can only show a very weak contrast under laser radiation, and the high requirements of laser marking are difficult to meet. In order to obtain a durable, high-definition, and high-quality marking effect in a short processing time, a laser sensitive additive is usually added to polyethylene.

Chinese patent application CN1108782A discloses a polyolefin resin-based marking composition containing a silicon compound, but a very small amount of the silicon compound is difficult to be uniformly dispersed in the polyolefin resin, resulting in that the laser marking effect is difficult to satisfy the actual demand. The Chinese patent application CN107513212A discloses a laser marking master batch for polyolefin, which is used in polyolefin according to a certain proportion and has good laser marking effect. However, the components of the laser marking master batch comprise a large amount of photosensitizer (accounting for 13-50% of the weight of the polyolefin resin), which can affect the processing performance of the optical cable sheath prepared from polyolefin, such as the optical cable sheath has a rough appearance.

Therefore, it is necessary to develop a polyethylene laser marking master batch suitable for the optical cable sheath.

Disclosure of Invention

The polyethylene laser marking master batch has good laser marking capability and is suitable for preparing optical cable sheaths.

The invention also aims to provide a preparation method of the polyethylene laser marking master batch.

The invention also aims to provide the application of the polyethylene laser marking master batch.

In order to solve the technical problems, the invention adopts the technical scheme that:

a polyethylene laser marking master batch comprises the following components in parts by weight:

45-70 parts of a polyethylene matrix,

10-15 parts of a polystyrene-based copolymer,

15-30 parts of lamellar structure mineral particles,

5-10 parts of a compatilizer,

1-2 parts of a lubricant,

0.1 to 0.3 part of a crosslinking sensitizer;

the silicon content of the lamellar structure mineral particles is more than or equal to 30 wt.%.

The inventor researches and discovers that the temperature rise of the material can obviously influence the definition of laser marking in the laser marking process, and the laser marking definition is relatively worse when the temperature rises more. The polystyrene-based copolymer has high absorptivity to laser beams, excellent heat resistance and good compatibility with polyethylene. In a polyethylene system, part of polystyrene-based copolymer is added, so that the heat resistance of the material can be improved, and a better laser marking effect can be obtained. The silicon content in the layered structure mineral particles is more than or equal to 30 wt%, so that excellent laser sensitivity can be brought, and laser beams can be absorbed in a near infrared range or a visible green laser range; due to the microscopic layered structure of the mineral particles, laser is reflected to a certain degree when the laser beam irradiates, and the temperature rise of the polyethylene material during laser marking can be reduced. The addition of the crosslinking sensitizer improves the heat-resistant temperature of the polyethylene laser marking master batch, and is favorable for better laser marking effect.

Preferably, the polyethylene matrix is high-melt-index polyethylene with a melt index of 18-25 g/10min, and the melt index test method is based on GB/T3682.1-2018, and a weight of 2.16kg is selected, and the temperature is 190 ℃.

Preferably, the polystyrene-based copolymer is one or more of acrylonitrile-butadiene-styrene copolymer (ABS), acrylate rubber-acrylonitrile-styrene copolymer (ASA), and Polystyrene (PS).

Preferably, the average particle diameter of the lamellar structure mineral particles is 100 to 300 μm.

If the average particle size of the layered structure mineral particles is too small, the laser sensitivity is too low; if the average particle diameter is too large, it is difficult to uniformly disperse the particles in the polyethylene system.

Preferably, the lamellar structure mineral particles are one or more of mica powder, talcum powder or kaolin.

Preferably, the compatibilizer is an ethylene-grafted maleic anhydride copolymer or a polyolefin elastomer-grafted maleic anhydride copolymer.

More preferably, the compatibilizer is an ethylene grafted maleic anhydride copolymer.

Preferably, the lubricant is a stearic acid-based lubricant.

Preferably, the crosslinking sensitizer is triallyl isocyanurate (TAIC) and/or trimethylolpropane trimethacrylate (TMPTA).

The invention also provides a preparation method of the polyethylene laser marking master batch, which comprises the following steps:

mixing a polyethylene matrix, a polystyrene-based copolymer, lamellar structure mineral particles, a compatilizer, a crosslinking sensitizer and a lubricant, adding the mixture into an extruder, and performing melt extrusion, cooling and granulation to obtain the polyethylene laser marking master batch.

The invention also protects the application of the polyethylene laser marking master batch in preparing the polyethylene material for the optical cable sheath.

The polyethylene material for the optical cable sheath comprises the following components: polyethylene resin, polyethylene laser marking master batch, carbon black, lubricating agent and antioxidant;

wherein the polyethylene laser marking master batch accounts for 5-10 wt% of the weight of the polyethylene resin.

Preferably, the polyethylene resin is high density polyethylene and linear low density polyethylene.

The polyethylene material for the optical cable sheath, which is prepared by compounding the high-density polyethylene and the linear low-density polyethylene, has better mechanical property.

Preferably, the melt index of the high-density polyethylene is 0.2-0.4 g/10min, and the test conditions are that a 2.16kg weight is selected according to GB/T3682.1-2018 and 190 ℃.

Preferably, the linear low density polyethylene has a melt index of 1.0-2.0 g/10min, and the test conditions are that a 2.16kg weight is selected according to GB/T3682.1-2018 and 190 ℃.

Preferably, the polyethylene material for the optical cable sheath comprises the following components in parts by weight:

35 to 60 parts of high-density polyethylene,

40 to 65 parts of linear low-density polyethylene,

5-10 parts of polyethylene laser marking master batch,

2.35 to 2.85 parts of carbon black,

0.5 to 1 part of a lubricant,

0.5-0.6 part of antioxidant.

The carbon black is one of channel carbon black, crystalline flake graphite or conductive carbon black.

Preferably, the carbon black is flake graphite or conductive carbon black.

Preferably, the average particle diameter of the carbon black is 50 to 100 μm.

The antioxidant is an antioxidant commonly used in polyethylene.

Preferably, the antioxidant is preferably pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) and/or tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168).

The invention also provides a preparation method of the polyethylene material for the optical cable sheath, which comprises the following steps:

mixing polyethylene resin, polyethylene laser marking master batches, carbon black, a lubricating agent and an antioxidant, adding the mixture into an extruder, and carrying out melt extrusion, cooling and granulation to obtain the polyethylene material for the optical cable sheath.

Preferably, the extruder is a double-screw extruder 75D, and is provided with a double-channel non-stop screen changer, and the filter screen is 80-120 meshes; the extrusion temperature is 190-210 ℃, the screw rotating speed is 450-550 HZ, and the feeding amount is 350-400 kg/h.

The invention also protects the application of the polyethylene material for the optical cable sheath in preparing the optical cable sheath.

Compared with the prior art, the invention has the beneficial effects that:

the invention develops a polyethylene laser marking master batch, which has excellent laser sensitivity through the synergistic effect of polyethylene, polystyrene-based copolymer, layered structure mineral particles, crosslinking sensitizer and other components. The polyethylene laser marking master batch is added into polyethylene according to the weight ratio of 5-10%, and the prepared polyethylene material is excellent in laser marking performance and suitable for preparing optical cable sheaths.

Detailed Description

The present invention will be further described with reference to the following embodiments.

The starting materials in the examples are all commercially available, and are specified below:

reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

Examples 1 to 8

Examples 1 to 8 provide polyethylene laser marking masterbatches, which are respectively marked as masterbatches a to H, and the content of each component of the polyethylene laser marking masterbatch is shown in table 1.

TABLE 1 contents (parts by weight) of each component in examples 1 to 8

The preparation methods of the polyethylene laser marking master batch of the embodiments 1 to 8 are all as follows:

mixing polyethylene, polystyrene-based copolymer, lamellar structure mineral particles, compatilizer, crosslinking sensitizer and lubricant, adding into an extruder, melting, extruding, cooling and granulating to obtain polyethylene laser marking master batch.

Examples 9 to 20

Embodiments 9 to 20 provide a polyethylene material for an optical cable sheath, where the content of each component of the polyethylene material for an optical cable sheath is shown in table 2.

TABLE 2 contents (parts by weight) of each component in examples 9 to 20

Comparative examples 1 to 8

Comparative examples 1 to 4 provide polyethylene laser marking master batches which are respectively marked as master batches A to H, and the addition amount of each component of the polyethylene laser marking master batch is shown in Table 3.

Table 3 addition amount (parts by weight) of each component in comparative examples 1 to 6

Comparative examples 7 to 15

Comparative examples 7 to 15 provide a polyethylene material for an optical cable sheath, and the addition amounts of the components of the polyethylene material for an optical cable sheath are shown in table 4.

Table 4 addition amount (parts by weight) of each component in comparative examples 7 to 15

Performance test

The polyethylene material for the optical cable sheath prepared in the above examples and comparative examples was subjected to a performance test.

The detection method specifically comprises the following steps:

extrusion appearance: extruding the polyethylene material for the optical cable sheath at 220 ℃ by using an annular mouth die, performing water cooling, traction by a tractor and rolling, and observing the appearance: the surface is smooth and flat, the glossiness is excellent, and the grade is A; the surface is smooth and flat, the glossiness is good, and the grade is B; the surface is slightly uneven, dark and dull and is C grade; the surface of a large part is uneven, dull, serious and dull, and is in D grade;

laser marking effect: the polyethylene material for the optical cable sheath is extruded into the optical cable by an optical cable forming extruder, and CO is adopted ₂ Marking by a laser marking machine, wherein the extrusion rate of the optical cable is 60m/min, marking is performed once every 1m, the marking character is a character of '5 m', the laser marking effect is observed, the character is regular and complete, and the laser marking effect is excellent; the characters are regular and complete, the edges are slightly unclear, and the laser marking effect is suboptimal; the characters are not correct and incomplete, and the laser marking effect is poor.

The test results of examples 9 to 20 are shown in Table 5, and the test results of comparative examples 7 to 15 are shown in Table 6.

TABLE 5 results of the Performance test of examples 9 to 20

9

10

11

12

13

14

Extruded appearance

Class A

Grade B

Grade A

Grade B

Effect of laser marking

Superior food

Youyou (an instant noodle)

Superior food

15

16

17

18

19

20

Extruded appearance

Class A

Grade A

Grade B

Grade A

Grade B

Grade A

Laser marking effect

Sub-optimal

Youyou (an instant noodle)

Superior food

Youyou (an instant noodle)

From the test results in table 5, it can be seen that the polyethylene materials for the optical cable sheaths prepared in examples 9 to 20 all have smooth extrusion appearance and clear laser marking effect.

Examples 9 to 16 are polyethylene materials for optical cable sheaths prepared using the master batches a to H, respectively, and it can be seen that: when the polystyrene-based copolymer in the polyethylene laser marking master batch is ABS or PS, the extrusion appearance of the polyethylene material for the optical cable sheath is better. Compared with other layered structure mineral particles, such as talcum powder or kaolin, the mica powder has smaller influence on the extrusion appearance of the polyethylene material for the cable sheath under the same addition amount. When the cross-linking sensitizer is TAIC or TMPTATAIC, the laser marking effect with correct and complete characters and clear marking edge can be achieved, wherein when the cross-linking sensitizer is TAIC, the laser marking effect is relatively better.

TABLE 6 Performance test results for comparative examples 7-15

In comparative example 7, the polyethylene material for the optical cable sheath prepared without adding the polyethylene laser marking master batch has poor laser marking effect. In comparative example 8, the addition amount of the polyethylene laser marking master batch was too large, which affected the extrusion appearance of the polyethylene material for the optical cable sheath.

In comparative example 9, the master batch J does not contain polystyrene based copolymer, and in comparative example 10, the ABS content of the master batch K is too high, so that the prepared polyethylene material for the optical cable sheath has poor laser marking effect, and the extruded appearance has a small amount of unevenness and dull gloss, which cannot meet actual requirements. In comparative example 11, the mineral particles used in the master batch L were calcium carbonate, which did not have a microscopic layered structure, and the laser marking sensitivity was low, and the laser marking effect of the polyethylene material for the optical cable jacket was poor. Comparative examples 12 to 14 are respectively that the polyethylene laser marking master batch mica powder used is excessive, contains no compatilizer and contains no crosslinking sensitizer, and the laser marked characters of the polyethylene material for the optical cable sheath are all not correct and incomplete, wherein the master batch N in the comparative example 13 contains no compatilizer, so that the extrusion appearance of the polyethylene material for the optical cable sheath is D grade.

In comparative example 15, the polyethylene laser marking master batch was not used, but mica powder was directly mixed with each component of the polyethylene material for the optical cable jacket, and the prepared polyethylene material for the optical cable jacket extruded with a poor laser marking effect had many uneven, severe dull, matte appearance portions.

It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. The polyethylene laser marking master batch is characterized by comprising the following components in parts by weight:

45-70 parts of a polyethylene matrix, 10-15 parts of a polystyrene-based copolymer, 15-30 parts of lamellar structure mineral particles, 5-10 parts of a compatilizer, 1-2 parts of a lubricant and 0.1-0.3 part of a crosslinking sensitizer;

the silicon content of the lamellar structure mineral particles is more than or equal to 30 wt.%;

the polystyrene-based copolymer is an acrylonitrile-butadiene-styrene copolymer and/or an acrylate rubber-acrylonitrile-styrene copolymer;

the mineral particles with the layered structure are one or more of mica powder, talcum powder or kaolin;

the crosslinking sensitizer is triallyl isocyanurate and/or TMPTA.

2. The polyethylene laser marking masterbatch according to claim 1, wherein the compatibilizer is an ethylene-grafted maleic anhydride copolymer or a polyolefin elastomer-grafted maleic anhydride copolymer.

3. The method for preparing the polyethylene laser marking master batch as claimed in any one of claims 1 or 2, which is characterized by comprising the following steps:

4. Use of the polyethylene laser marking masterbatch according to any one of claims 1 or 2 for preparing a polyethylene material for optical cable sheaths.

5. The polyethylene material for the optical cable sheath is characterized by comprising the following components:

polyethylene resin, the polyethylene laser marking master batch of any one of claims 1 or 2, carbon black, a lubricant, an antioxidant; wherein the polyethylene laser marking masterbatch of any one of claims 1 or 2 comprises 5 to 10 wt.% of the polyethylene resin;

the polyethylene resin is high density polyethylene and linear low density polyethylene.

6. Use of a polyethylene material for a cable jacket according to claim 5 for the preparation of a cable jacket.